CN113522363A - 水凝胶中金属离子改性mof微/纳结构的制备方法及应用 - Google Patents
水凝胶中金属离子改性mof微/纳结构的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种水凝胶中金属离子改性MOF微/纳结构的制备方法及其应用,属于有机纳米光催化领域。本发明将卟啉配体与金属团簇反应得到卟啉MOF微/纳结构,然后将其与海藻酸钠(SA)水溶液共混后冰冻成型,并置于过量二价金属盐(M2+)溶液进行交联固化,得到SA‑M2+‑MOF水凝胶球。利用交联金属离子与卟啉分子配位的方法,在有效改性MOF微/纳结构的同时,使之均匀、牢固嵌入SA水凝胶球骨架中,提高其可回收利用性。本方法简单易行,为有机纳米材料的可控、整体组装提供了实验基础。通过对所得的SA‑M2+‑MOF在光催化降解有机染料的应用进行研究,结果显示该结构具有高效的光催化活性。为广泛应用于污染治理、能源枯竭提供了可能性。
Description
技术领域
本发明属于有机纳米光催化领域,具体涉及一种水凝胶中金属离子改性卟啉MOF微/纳结构的制备方法及其应用。
背景技术
随着经济社会的发展,化石能源广泛使用和消耗,威胁人类生存的环境污染和能源危机日益严峻,有必要寻找一种低成本的清洁可再生能源,利用新型高效技术解决环境问题。
有机半导体光催化剂相比无机半导体材料,价格更加低廉,制备工艺更加简单方便,且因其结构上的多样性与宽的太阳光谱吸收,而表现出优异的可见光催化降解污染物性能(Organic Photocatalysts for the Oxidation of Pollutants and ModelCompounds,M.Luisa Marin,Lucas Santos-Juanes,Antonio Arques,CHEMICAL REVIEWS,2011,1710-1747.)。近年来,金属有机框架材料(metalorganic frameworks,MOFs)因其独特的结构优势,如多孔性、结构可调节性、可功能化等,有助于研究者从化学结构层面来设计光催化剂(Metal-organic frameworks(MOFs)-based efficient heterogeneousphotocatalysts:Synthesis,properties and its applications in photocatalytichydrogen generation,CO2 reduction and photodegradation of organicdyes.Ch.Venkata Reddy,Kakarla Raghava Reddy,V.V.N.Harish.INTERNATIONALJOURNAL OF HYDROGEN ENERGY,2020,7656-7679.)有机结构纳米化后的比表面积大、孔隙率高能够吸附更多的外部物质进行降解;载流子迁移率提高,能够表现出更好的降解能力;解决了有机均相体系活性分子回收再利用的问题,提高材料体系重复使用率。
卟啉MOF作为具有良好光电性质的新型光催化剂,既具有卟啉拓宽光谱响应范围、降低光生电子-空穴复合率的独特优势,又具有MOF材料的多孔道、孔道尺寸可调节、比表面积大的优势。越来越多的研究表明纳米化能够改性卟啉MOF的形貌、降低尺寸提高降解效率,重复使用率(Metal–Organic frameworks for the exploitation of distancebetween active sites in efficient photocatalysis.Gong X,Shu Y,JiangZ.ANGEWANDTE CHEMIE,2020,5326-5331.)但是MOF粉末的可回收性较差,采用各种方法合成的MOF负载水凝胶整体性能较差,存在MOF脱落等问题。
目前还没有文献和专利报道水凝胶中金属离子改性MOF微/纳结构的制备方法,并提出将其应用于光催化领域。
发明内容
本发明要解决的第一个技术问题在于提供了一种水凝胶中金属离子改性MOF微/纳结构的制备方法。针对现有的MOF纳米结构制备方法中,自组装过程过快导致聚集体尺寸过大、晶型不完善等问题,本发明提供一种水凝胶中金属离子改性MOF微/纳结构的制备方法,可以有效地控制形貌、尺寸,完善晶型和孔结构,并提高其分散性及可回收性。
本发明要解决的第二个技术问题在于提供一种是卟啉MOF水凝胶的应用。
解决上述第一个技术问题,本发明采用一种水凝胶中金属离子改性MOF微/纳结构的制备方法,其特征在于,制备过程如下:通过传统溶剂热反应得到卟啉MOF微/纳结构,然后将其与SA水溶液混合,搅拌均匀后冷冻定型,并置于过量二价金属盐溶液进行交联固化得到SA-M2+-MOF水凝胶球。
如上所述一种水凝胶中金属离子改性MOF微/纳结构的制备方法,其特征在于,包括以下步骤:
S1:制备卟啉MOF微/纳结构
将ZrCl4和卟啉(TCPP)基体溶解在N,N-二甲基甲酰胺(DMF)中,并加入乙酸和去离子水,于室温下搅拌均匀,随后将均匀溶液100-200℃加热5-15小时。
S2:金属离子改性法制备SA-M2+-MOF水凝胶球:
将制备好的卟啉MOF微/纳结构分散在去离子水中,并与SA水溶液混合均匀,将混合溶液冷冻定型后置于10-100ml金属盐溶液交联固化。
进一步地,S1中所述的卟啉分子为5,10,15,20-四-(4-羧基苯基)卟啉(TCPP)。
进一步地,S1中所述ZrCl4和TCPP添加量各为0-20mg,DMF添加量为1-10mL。
进一步地,S2中所述SA添加量为10-100mg,卟啉MOF添加量为1-10mg。
进一步地,S2中所述插层离子为Zn2+、Co2+、Cu2+、Fe2+、Pt2+、Ru2+、Ba2+、Pb2+、Ra2+、Sn2 +、Mn2+、Ni2+等二价金属阳离子,金属离子浓度为0.1-0.5mol/L,体积为10-100mL。
进一步地,所述搅拌为磁力搅拌,搅拌时间为5-30分钟。
进一步地,S2中得到的卟啉MOF微/纳结构尺寸约50-5000nm,SA-M2+-MOF水凝胶形状为球状。
为解决上述第二个技术问题,本发明所述SA-M2+-MOF水凝胶球是作为光催化剂应用于光降解有机物中。
本发明的有益效果
1.本发明通过简单易行的溶剂热反应法得到形貌尺寸均一的卟啉MOF微/纳结构。
2.本发明通过简单易行的金属离子改性法得到的SA-M2+-MOF水凝胶球,在降解亚甲基蓝(MB)的应用上体现出高效的光催化性能,水凝胶球的整体结构大大提高光催化剂的可回收性。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图。
图1.实施例1中传统溶剂热反应制备的卟啉MOF微/纳结构的扫描电镜(SEM)照片。
图2.实施例2中Zn2+作为改性金属离子制备SA-M2+-MOF水凝胶球照片。
图3.实施例2中Zn2+作为改性金属离子制备SA-M2+-MOF水凝胶微球扫描电镜(SEM)照片。
图4.实施例1中传统溶剂热反应制备的卟啉MOF微/纳结构和实施例2中Zn2+作为改性金属离子制备的SA-M2+-MOF水凝胶球光催化降解MB效果图。
具体实施方式
实施例1:
本次实施例所使用的卟啉为TCPP,由北京百灵威科技有限公司提供,使用前未做进一步处理,其结构式如式1所示:
具体制备步骤如下:
1)将0-20mg ZrCl4和0-20mg TCPP溶解在1-10mL DMF溶液中,然后加入50-200μL乙酸和10-100μL去离子水。
2)混合溶液在室温下磁力搅拌5-30分钟,随后将溶液密封并100-200℃加热。反应5-15小时后进行离心、干燥、收集样品。图1可见卟啉MOF尺寸为100-800nm。
性能测试:
1)称取传统溶剂热反应收集到的卟啉MOF粉末1-20mg加入到10-100mL,0.01-0.1mM的MB溶液中,暗条件进行吸附-解吸附平衡后,在模拟太阳光(光照强度100mW/cm2)下照射100分钟,隔10分钟取样进行紫外-可见吸收光谱测试;对于实施例1中所制备的样品测试性能结果如图4所示。
实施例2:
1)配置浓度过量的Zn2+盐溶液10-100ml,称取SA粉末10-100mg加去离子水1-10ml。称取实施例1得到的卟啉MOF粉末1-10mg,加水1-10ml配置MOF分散液。
2)将1)中SA水溶液和卟啉MOF分散液混合,搅拌5-30分钟后冷冻定型,加入1)中的Zn2+盐溶液中,得到的SA-M2+-MOF水凝胶球见图2和图3。
性能测试:
1)将金属离子改性法得到的SA-M2+-MOF水凝胶球加入到10-100mL,0.01-0.1mM的MB溶液中,暗条件进行吸附-解吸附平衡后,在模拟太阳光(光照强度100mW/cm2)下照射100分钟,隔10分钟取样进行紫外-可见吸收光谱测试;对于实施例1中所制备的样品测试性能结果如图4所示。
实施例3:
重复实施例2,其不同仅在于步骤1)中的金属离子为Co2+。
实施例4:
重复实施例2,其不同仅在于步骤1)中的金属离子为C u2+。
实施例5:
重复实施例2,其不同仅在于步骤1)中金属离子为Fe2+。
实施例6:
重复实施例2,其不同仅在于步骤1)中金属离子为Pt2+。
实施例7:
重复实施例2,其不同仅在于步骤1)中金属离子为Ru2+。
实施例8:
重复实施例2,其不同仅在于步骤1)中金属离子为Ba2+。
实施例9:
重复实施例2,其不同仅在于步骤1)中金属离子为Pb2+。
实施例10:
重复实施例2,其不同仅在于步骤1)中金属离子为Ra2+。
实施例11:
重复实施例2,其不同仅在于步骤1)中金属离子为Sn2+。
实施例12:
重复实施例2,其不同仅在于步骤1)中金属离子为Mn2+。
实施例13:
重复实施例2,其不同仅在于步骤1)中金属离子为Ni2+。
通过对比实施例1与2,可以看出,通过离子改性,可以有效改善卟啉MOF分子自组装结构,在降低结构大小,完善晶型方面有重要作用,从而提高光催化活性和光催化剂的回收利用性能。
Claims (9)
1.一种水凝胶中金属离子改性MOF微/纳结构的制备方法,其特征在于,制备过程如下:通过传统溶剂热反应得到卟啉MOF微/纳结构,然后将其与SA水溶液混合,搅拌均匀后冷冻定型,并置于过量二价金属盐溶液进行交联固化得到SA-M2+-MOF水凝胶球。
2.根据权利要求1所述的水凝胶中金属离子改性卟啉MOF纳米结构的制备方法,其特征在于,所述制备方法具体包括以下步骤:
S1:制备卟啉MOF微/纳结构
将ZrCl4和卟啉基体溶解在N,N-二甲基甲酰胺(DMF)中,然后加入乙酸和去离子水,并在室温下搅拌,随后将均匀溶液100-200℃加热5-15小时;
S2:金属离子改性法制备SA-M2+-MOF水凝胶球
将S1中得到的卟啉MOF微/纳结构分散在水中,并与SA水溶液混合,室温搅拌均匀后,冷冻定型,并置于过量二价金属盐交联固化,得到SA-M2+-MOF水凝胶球。
3.根据权利要求2所述的制备方法,其特征在于,所述的卟啉分子为5,10,15,20-四-(4-羧基苯基)卟啉(TCPP)。
4.根据权利要求2所述的制备方法,其特征在于,所述S1中ZrCl4和TCPP添加量各为0-20mg,DMF添加量为1-10mL。
5.根据权利要求2所述的制备方法,其特征在于,所述S2中SA添加量为10-100mg,卟啉MOF添加量为1-10mg。
6.根据权利要求2所述的水凝胶中金属离子改性MOF微/纳结构的制备方法,其特征在于,所述金属离子为Zn2+、Co2+、Cu2+、Fe2+、Pt2+、Ru2+、Ba2+、Pb2+、Ra2+、Sn2+、Mn2+、Ni2+二价阳离子,金属离子浓度为0.1-0.5mol/L,体积为10-100ml。
7.根据权利要求2所述的水凝胶中金属离子改性MOF微/纳结构的制备方法,其特征在于,所述搅拌为磁力搅拌,搅拌时间为5-30分钟。
8.根据权利要求2所述的水凝胶中金属离子改性MOF微/纳结构的制备方法,其特征在于所得到的卟啉MOF微/纳结构尺寸为50-5000nm,SA-M2+-MOF水凝胶形状为球状。
9.根据权利要求2所述的制备方法得到的SA-M2+-MOF水凝胶球的应用,其特征在于所述SA-M2+-MOF水凝胶球是作为光催化剂应用于光催化降解有机物。
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